Anthraquinone dyestuffs



United States Patent U.S. Cl. 260329.2 6 Claims ABSTRACT OF THE DISCLOSURE Very stable dyes for polyamides, acetates and polyesters, have the formula u E (J E) \H/ I Rr-SOz-Ra 0 NH A s wherein R signifies alkylene having 1 to 6 carbon atoms, R signifies phenyl, alkyl having 1 to 6 carbon atoms, phenyl alkyl in which the alkyl has up to 6 carbons or alkyl phenyl in which the alkyl has up to 6 carbons, R and R may also be linked with each other to form a tetramethylene sulfone ring with the S0 R is hydrogen or lower alkyl, and the carbons in the phenyl nucleus A as well as in R and R may be substituted by Cl, Br, OH or lower alkoxy.

The present invention is concerned with new anthraquinone dyestuffs and synthetic materials dyed with them.

The dyestufis of the present invention have the general formula wherein R signifies alkylene having 1 to 6 carbon atoms, R signifies phenyl, alkyl having 1 to 6 carbon atoms, phenyl alkyl in which the alkyl has up to 6 carbons or alkyl phenyl in which the alkyl has up to 6 carbons, R and R may also be linked with each other to form a tetramethylene sulfone ring with the S0 R is hydrogen or lower alkyl, and the carbons in the phenyl nucleus A as well as in R and R may be substituted by Cl, Br, OH or lower alkoxy. Lower alkyl and lower alkoxy groups have 1 to 3 carbon atoms.

The foregoing dyes are obtained by condensing 1,4-dihydroxy-anthraquinone, its leuco-compound, or a 1-hydroxy-4-chloroor -bromo-anthraquinone, with an amine having the formula wherein R and R have the meaning given above. They are also obtained when 1-hydroxy-4-amino-anthraquinone is condensed with the chloro or bromo counterpart of the foregoing amine.

3,525,639 Patented Sept. 1, 1970 The dyestuffs of the present invention are especially suited for dyeing and printing synthetic materials, such as polyamide, cellulose acetate, or cellulose triacetate, and more particularly polyester materials, such as polyethyleneglycol terephthalate. When operating according to the usual dyeing and printing processes, they yield deep dyeings and full prints with excellent fasteness properties, especially an outstanding fastness to light and sublimation. The above-mentioned materials can be printed in such manner that the printed articles are steamed in the presence of a carrier at temperatures of about to 100 C., or in the absence of a carrier at about 110 to 140 C., or treated at about 170-230 C. according to the so-called process of thermofixing. Dyeing is also suitably effected from an aqueous suspension in the presence of carriers at temperatures of about 100 to 110 C., in the absence of carriers between about 110 to 140 C., as well as according to the so-called process of thermofixing at about 170 to 230 C.

By the term carriers is understood such compounds as are described for example in the periodical Melliand Textilberichte 1961, page 1275, and 1962, page 156.

The amines required as initial products, are preferably produced by nitrating and reducing in the usual manner the addition products of styrene to sulfones as described in US. patent application Ser. No. 575,229 filed Aug. 26, 1966, now US. Pat. No. 3,448,111, or the condensation products obtainable according to H. Bohm and l-L-G. Grove in the periodical Chemische Berichte (1952) on page 415, from aryl-alkylchlorides and sodium salts of organic sul-finic acids.

The following examples are given for the purpose of illustrating the present invention. The parts and percentages given are by weight, and the temperatures are in degrees centigrade.

EXAMPLE 1 A mixture consisting of 450 parts water, 27.0 parts 1,4- dihydroxy-anthraquinone, 27.0 parts leuco-1,4-dihydroxyanthraqunione, 54.3 parts 4-aminophenyl-propyl methyl sulfone, and 1.5 parts boric acid is heated to to for 24 hours. The mixture now contains besides the desired dyestufi the leuco-compound of this dyestuif, which leucocompound is oxidized by introducing air for 8 hours after the batch has been further admixed with 1.5 parts copper acetate and 9.0 parts piperidine, and heated to 60. The dye is now filtered off with suction and rinsed with water. To remove the non-reacted 1,4-dihydroxy-anthraquinone, the dye is mixed with 1.000 part water and 234 parts sodium hydroxide solution of 33 B., and stirred at 95 for one hour. The dye is again filtered off with suction, washed neutral with water, and dried. It is a blue powder dissolving in concentrated sulfuric acid with a greenish blue color.

The 4-aminophenyl-propyl methyl sulfone is prepared by adding dimethylsulfoxide to styrene, oxidizing the resultant sulfoxide to the corresponding sulfone, nitrating said sulfone and reducing the nitro group thus introduced to obtain the amine.

In the usual manner, 0.3 part of the above prepared and purified dye are finely divided and dispersed in 3.000 parts water. parts of a polyethylene-glycol terephthalate fabric are put into the dyebath thus obtained, and the fabric is dyed at temperatures ranging between and for 1 /2 hours. After the subsequent rinsing process and the reductive after-treatment with a 0.2% alkaline sodium dithionite solution at 6070 for 15 minutes and the rinsing with Water and drying, a reddish blue dyeing is obtained having very good fastness properties.

Dyestuffs with similar valuable tinetorial properties are obtained by replacing the 4-aminophenyl-propyl 3 methyl sulfone of the above example by an equimolecular amount of any of the following amines:

3-aminobenzyl ethyl sulfone 4-aminobenzyl methyl sulfone 4-aminobenzyl hydroxy-ethyl sulfone 4-aminophenylethyl methyl sulfone 3-methyl-4-aminobenzyl ethyl sulfone 2-chloro-4-aminobenzyl methyl sulfone 4-aminophenyl-propyl pentyl sulfone 3-(p-an1inophenyl)-3-methyl-propyl methyl sulfone or by a mixture of equal parts of p-aminobenzyl 3-hydroxy-propyl sulfone and p-aminobenzyl Z-hydroxy-isopropyl sulfone.

EXAMPLE 2 A mixture consisting of 100 parts water, 50 parts ethanol, 12.0 parts 1,4-dihydroxy-anthraquinone, 6.0

parts leuco-1,4-dihydroxy-anthraquinone, and 20.3 parts 1-(4'-aminophenylethyl)-tetramethylene-sulfone, having and 9.0 parts of boric acid is heated to simmering for 24 hours to form the desired dyestufli. After cooling down, the dyestuff is filtered off with suction, rinsed first with ethanol and then with water. In order to eliminate the non-reacted 1,4-dihydroxy-anthraquinone, the dye is subjected to an alkaline aftertreatment, as described in Example 1. After drying, the dyestufi is a dark-blue powder that dissolves in concentrated sulfuric acid with a greenish blue color.

25 parts of the purified dye in finely divided form, are made up into 1000 parts of a printing paste which contains 60 parts of tragacanth as a thickener, and 75 parts of the sodium salt of a sulfonated castor oil. A polyester textile is printed with this paste, dried, fixed in a thermo-fixing frame at 215 for 60 seconds, and then rinsed with water and dried, leaving the fabric with a deep reddish blue print having excellent fastness properties.

Prints of equally very good fastness properties are obtained by replacing the 1 (4 aminophenyl ethyl)- tetramethylenesulfone of this example by an equimolecular amount of A mixture consisting of 100 parts nitro-benzene, 9.6

parts 1 hydroxy 4 amino anthraquinone, 15.0 parts 4-bromo-phenylpropyl methyl sulfone, 6.0 parts sodium carbonate, 4.4 parts sodium acetate, 0.5 part copper acetate, 0.5 part copper powder are heated up to 210 for 24 hours. Subsequently, the nitrobenzene is removed by steam distillation and the desired dye is filtered off with suction, rinsed with water, and dried. After recrystallization from glacial acetic acid, it forms dark-blue crystals which melt at 169 to 171 and dissolve in concentrated sulfuric acid with a greenish blue color.

The dye thus formed is identical with that of Example 1. When applied to polyester fabrics it yields dyeings 4 which, with regard to their tinctorial properties, are not distinguishable from those of Example 1.

What is claimed is: 1. An anthraquinone dyestuif of the formula wherein R signifies alkylene having 1 to 6 carbon atoms, R signifies phenyl, alkyl having 1 to 6 carbon atoms, phenyl alkyl in which the alkyl has up to 6 carbons and alkyl phenyl in which the alkyl has up to 6 carbons, R and R may also be linked with each other to form a tetramethylene sulfone ring with the S0 R is hydrogen or lower alkyl, and the carbons in the phenyl nucleus A as well as in R and R may be substituted by Cl, Br, OH or lower alkoxy.

2. A dyestuff according to claim 1 in which R is a para-positioned trimethylene and R is methyl.

3. A dyestuif according to claim 1 in which R is a para-positioned trimethylene and R is phenyl.

4. A dyestuif according to claim 1 and having the formula 5. A dyestuif according to claim 1 and having the formula 6. A dyestufi according to claim 1 and having the formula References Cited UNITED STATES PATENTS OTHER REFERENCES Venkataraman: The Chemistry of Synthetic Dyes, vol. II (Academic Press, N.Y., 1952), p. 8125.

HENRY R. JILES, Primary Examiner C. M. SHURKO, Assistant Examiner U.S. Cl. X.R. 839, 40; 260-373 

